Esters of 3-(2,2-tetramethylene ethenyl)-2,2 - dimethylcyclopropanecarboxylic acid

ABSTRACT

DESCRIBED ARE ESTERS OF CERTAIN CARBOCYCLIC ALCOHOLS WITH 3-(2,2-TETRAMETHYLENE ETHENYL)-2,2-DIMETHYLCYCLOPROPANECARBOXYLIC ACID AND A METHOD FOR PREPARING SAME IN THE TRANSISOMERIC FORM. THESE ESTERS POSSESS UNIQUE INSECTICIDAL PROPERTIED AND ARE USEFUL AS SUCH IN HOME, GARDEN AND AGRICULTURAL APPLICATION.

United States Patent 3,679,667 ESTERS 0F 3-(2,2-TETRAMETHYLENE ETHENYL)-2,2 DIMETHYLCYCLOPROPANECARBOXYLIC ACID Wayne I. Fanta, ColerainTownship, Hamilton County, Ohio, assignor to The Procter & GambleCompany, Cincinnati, Ohio No Drawing. Filed Mar. 27, 1970, Ser. No.23,513

Int. Cl. C07d 5/34 US. Cl. 260-240 R Claims ABSTRACT OF THE DISCLOSUREDescribed are esters of certain carbocyclic alcohols with3-(2,2-tetramethylene ethenyl) 2,2 dimethylcyclopropanecarboxylic acidand a method for preparing same in the transisomeric form. These esterspossess unique insecticidal properties and are useful as such in home,gar den and agricultural applications. 6

BACKGROUND OF THE INVENTION This invention relates to novel insecticidalcompounds, to a process for preparing same in the trans-form and toinsecticidal compositions containing said compounds as an essentialactive ingredient.

Current trends in the chemical control of insects call for inherentlysafer materials which degrade very rapidly to non-toxic substances oncetheir purpose 'is accomplished. The safety of the widely usedchlorinated hydrocarbons, notably DDT, is currently under questionlargely because of their poor biodegradability and concomitantpersistence. Accordingly, there is a great demand for alternative broadspectrum insecticides which are suitable for the high volume usageentailed in agricultural applications. At the same time it is necessaryfor new insecticides to exhibit a low order of toxicity to warm-bloodedanimals. Of the several insecticide classes which demonstrate lowmammalian toxicity and good biodegradability,

it has long been recognized that pyrethrum, a naturally occurringinsecticidal mixture, possesses these :desirable properties. In additionto the safety advantages, this natural mixture yields rapid knock-downand kill of a broad spectrum of insects; however, it is unstable tolight, air, and heat, and is very expensive. The most active componentof pyrethrum is pyrethrin Land a' number of analogous compounds havebeen proposed for insecticidal use. Allethrin, the -most widely usedsynthetic pyrethrinlike insecticide, while more stable to light and heatthan pyrethrum, is nevertheless expensive, a defect which is compoundedby the fact that this substance is not synergized by the low costsynergizing agents such as piperonyl butoxide which are typically usedin insecticidal compositions. Because of instability, high cost andlimited supply,

genetic mechanisms capable of detoxifying any particular insecticidalcompound. In any event, it is desirable to have included in theinsecticidal armamentarium, compounds which may be utilized once a givenclass of insects is found which no longer respond to conventionalinsecticidal compounds.

"It is therefore an object of this invention to provide novelinsecticidal'compounds which are biodegradable, effect rapid knock-downand kill of a broad spectrum of insects, possess low mammalian toxicity,and are less susceptible to detoxification by insects than is pyrethrum.

It is a still further object of thisinvention to provide a novelsynthesis of thet'ransform' of insecticidal esters of3-(2,2-tetramethylene ethenyl)-2,2-dimethy1cyclopropanecarboxylic acids.These and other objects are obtained by the present invention as willbecome apparent from the following disclosure.

DETAILED DESCRIPTION OF THE INVENTION The novel compounds of the presentinvention have the formula:

. CH4, CH:

I uni-0H, i 0

' o;on-o fi on-ii-on H -CH: wherein R is a radical selected from thegroup consisting wherein R is a member selected from the groupconsisting of hydrogen, halogen, short-chain alkyl (e.g., methyl, ethyl,propyl), and short-chain alkoxy (e.g., methoxy, eth- 1 oxy,propoxy),'ary1, halogen, N0 NHg, and COCH the use of pyrethrum andpyrethrin-like insecticides in garden and agricultural applications hasbeen precluded or seriously limited.

At the same time, it is well known that certain insects, in time, becomeimmune to the insecticidal properties of various chemical agents. To beeflicient an insecticide should be able to resist detoxification by theinsect. The biological mechanism whereby insects are capable ofdetoxifying the various types of insecticidal compounds is not known.However, it has been suggested that in compounds which are analogous topyrethrin, e.g., allethrin, one mode of detoxification may involveoxidation of one or both of the methyl groups on the methylpropenyl sidechain of the chrysanthemic acid moiety present in that compound.Additionally, it is possible that, as with other biological systems,insects may in time develop new bio- Thus, the esters of3-(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acidwith allethrolone, cinerolone, pyrethrolone, Z-indanol, diandtetrahydro-2-in danol, S-substituted -2-indanols, 3-coumaranol,5-substituted-3-coumaranols and 5-benzyl-3-furfuryl methanol arecompounds encompassed by the present invention. Especially preferred arethe esters of 3-(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid and allethrolone, Z-indanol, 3-coumarano1 and5-benzy1-3-f furyl methanol. 6 r

The unique structural features of the cyclopropyl carboxylic acids ofthis invention results in the formulation of geometrical isomers of thecis-trans-type. It has been recognized that in most cases the transacids afford more active insecticidal compositions when esterified witha given alcohol than do the cis acids However, separation of the transfrom the cis form of the acid or acid esters is difiicult to accomplisheconomically. However, it has been found that the intermediate aldehydeester mixture formed through ozonalysis of cis-trans-ethylChrysanthemate during the synthesis of the novel acids of this inventionis easily separable into its cisand trans-isomers by simpledistillation. As later described, this aldehyde ester is suitable forconversion into the trans form of the acids of this invention and thenceto their insecticidal ester compounds having the acid portion in thetrans form.

The compounds of this invention are prepared by esterification of3-(2,2-tetramethylene ethenyl)-2,2=dimethylcyclopropanecanboxylic acidwith the desired alcohol. The 3-(2,2-tetramethyleneethenyl)-2,2-dimethylcyclopropanccarboxylic acid is prepared accordingto the general reaction sequence below:

- 8.4 (m, 4, 2-oH,- 8.50(t, 3, 1:6 Hz., oc:H,cg,

the ozonide to form Aldehyde I Reaction of Aldehyde I with the ylidformofthe Wittig reagent of the ,type

.- out-on,

(phenyl): P+CH X" i orrr- 11,

wherein X=halogen, results in an ester having the desired substitutionfor the isopropyl group of the isobutylene unit. This esterisiconvertedto the acid by standard procedures. In the practiceof theprocess aspect of this invention; the AldehydesI can be separated, nto1ts.c1s

Specifically, "3-(2,2-tetramethyleneethenyD-LZ-dimethylcyclopropanecarboxylic acid is prepared as follows:

ENE E'IfI-IENYL) 2,2 DIMETHY I 1 .-Cis/trans 3-carboethoxy 2,2dimethylcyclopropane'carboxaldehyde (Aldehyde I): A solution of 42.4gofethyl. chrysanthemate in 24 ml. MeOH- and 12 ml. H O was subjected tothe ozonalysis procedure of Eschinasi, U.S.-Pat. 3,023,244, for 6hrs..at 0.03 cu. ft./min. The total was added to. 13 g. zinc dust in 100ml. H 0 and 10 ml. benzene, stirred, treated 20 min. with 32 g. 62% H 80stirred 10 min. after addition and extracted with ether. The ether. waswashed with 2% NaOH, sat.

Natl-[C0 isat. NaI, brine until neutral and. dried (MgSO After,removalof low boiling solvents, the

colorless residual oil was fractionally distilled on an 181! spinningband column yielding: trans-3-carboethoxy-2,2-

dimethylcyclopropanecarboxaldehyde: B.P. 5461 (0.55

mm.); IR(neat) 3.34, 5.78, 5.85, 8.49;; nmr (C01 1- 0.0 (s, 1, CHO),5.36 (q, 2, 1:6 Hz., -OCH C-I-I 7.0 (s, 2, CH), 8.7, and. 8.74 [2s, 6,C(CH 8.78 (t, 3, i=6 Hz,--OCH CH glc indicated no less than 97% purity.Continued distillation .gave cis-3-carboethoxy' 2,2dimethylcyclopropanecarboxaldehydc: B.P. 61- (0.55 mm.) 55 (0.45 mm.);IR (neat) 3.38, 5.78,

indicated approx. 85% purity.

Step 2.--Trans-ethyl 3-(2,2-tetramethylene ethenyl)-2,Z-dimethylcyclopropanecarboxylate: A mixture of 3.25 g. of NaH (60%mineral oil dispersion) in 125 ml. dry

DMSO was blanketed with argon and heated at 75 C. for 1 hour. Thereaction was cooled to 510 C. and charged with 32.4 g. oftriphenylcyclopentylphosphonium bromide prepared according to Ramirez etal., J. Amer. Chem. Soc., 79, 67 (1957), and stirred for 30 min. whilewarming to room temperature. A solution of 4.5 g. of trans-B-carboethoxy2,2 dimethyleyclopropanecarboxaldehyde in 65 m1. of dry DMSO was addedand the resultingreaction stirred at room temperature for 3 hours,poured into brine and extracted with pentane. The com- -Ibined pentaneextracts were washed with H O, dried 8.50-and 8.70 [2s, 6, C(C massSpectrum Parent ion;-m/e 222, L,

Step 3.'Trans-3-(2,2-tetramethylene etheny1)- 2,2-di--methylcyclopropanecarboxylicacid: A solution of 4.6 g.

of trans ethyl. 3-(2,2-tetramethyleneethenyl)-2,2-'dimethylcyclopropanecarboxylate in 65 ml. 95% EtOH wassaponified in standard fashion by heating with KOH followed by an acidwork-up. Work-up afforded 4.4g. of acid which was suitable for furtheruse. Alternatively, Aldehyde I is not separated into its cisandtrans-isomers in the above process but is directly alkylated with theWittig reagent to afford the cis-transacid and, thence, thecis-trans-acid chloride mixture.

. The alcohols used in the preparation of the compounds of thisinvention are prepared as follows:

r (I) Z-indanols: Commercially available Z-indanone is reduced withlithium. aluminum hydride to provide the parent alcohol, Z-indanol,according to the method of I-Iiickel. and Bollig, Chem. Ber., 86, 1137(1953). The partially reduced .Z-indanols are prepared by the wellknownBirch-type reductions. Likewise, various substituted Z-indanones havingfunctional groups R, as previously noted, are reduced to the respectiveS-Substituted- 2-indanols; for example, 5-substituted indanols such asS-ethyl, S-methoxy, S-nitro and 5-acetyl indanols may be preparedaccording to the procedures of Inamoto et al., Can. Iour. Chem, 45,1185, 1192 (1967), and reduced with lithium aluminum hydride tov thealcohols as described supra. The tollowing specific Z-indanols are prepared in this manner. p

: 7(a) 2-indanol: A solution of commercial Z-indanone (5; g., 3.78'X103mol.) in ether (50 ml.) is added dropwiseover a 40 minute period to astirred suspension of lithium aluminum hydride (1.44 g., 378x10. mol.)in

ether (50 ml.). The resultant mixture is stirred at reflux for 16 hours.The reaction mixture is cooled and 1 'N sodium hydroxide (4.5 ml.) isadded. The mixture is filtered, the solids washed well with ether, andthe combinecl filtrates evaporated to give a white solid. The solid isrecrystallized from a mixture of pentane (50 ml.) and ether (25 ml.).The resulting white solid is homogeneous on 20% FFAP at 200 C.; M.P.68-69" C.;

ir ouch emf (OH) nmr(CDCl -r 8.3 (S, 1, g), 7.0 (AB q, 4, 1 =16 Hz., CgCHOH-CH each line of quartet further split, .1 =6 Hz. for downfield halfand i=3 Hz. for upfield half of quartet); 5.4 (multiplet, 1, Cg OH), and2.9 (S, 4, aromatic hydrogens).

- (b) 4,5,6,7-tetrahydro-2-indanol: Lithium (1.44 g., 2.1 10- mol.) isadded to a stirred mixture of n-propylarnine (65 ml.) and Z-indanol (2.5g., 1.86 10 mol.) and theresultant mixture is stirred for 2-2 hours.Solid ammonium chloride is Iadded until no further reaction occurs. Thisis followed by the addition of water (100 ml.) and ether (100 ml.). Thelayers are separated and the organic layer dried (MgSO and evaporated.to give a red liquid. Distillation yields a pink liquid [B.P. 110-1 14C./11 mm.] which is sublimed twice and the resultant solidrecrystallized twice from hexane to yield a solid: greater than 95% pureon 20% FFAP at 200 C.; M.P. 49-50.5 C.; e

munch) 3440,cm." (OH) nmr(CDCl '1' 7.2-8.4 (complex area, 13), and 5.6(complex multiplet, 1, C'H -CgOHCH ,(H) 3-coumaranols: A preferred classof compounds for use in the practice of the instant invention isprepared by the, reaction of salicylaldehyde or a 5-substitutedsalicylaldehyde with dimethyloxosulfonium methylide to secure thecorresponding 3-coumaranol in accordance with the method described by B.Holt and P. A. Lowe, Tetrahedron Letters, #7, 683 (1966) as detailed byE. 1. Corey and. M. Chaykovsky J. Amer. Chem. Soc., 87, 1353 (1965). Thefollowing coumaranols were prepared in this manner. g

(a) 3-coumaranol: According to the, procedure of Corey and Chaykovsky, anitrogen blanketed mixture of 2.52 g. (0.09 mol.) of sodium hydride (asa 61% mineral oil dispersion) and 14.1 g. (0.064 mol.) oftrimethyloxosulfonium iodide was stirred and treated dropwise over 15min. with 70 ml. of dry dimethyl sulfoxide. The reaction mixturewasthencooled to C. and a solution of 7.32 g.- (0.06 mol.) of salicylaldehydein 30 ml. of dry dimethyl sulfoxide was added in one portion withstirring. After 5 the cooling bath was removed and stirring wascontinued at room temperature for 2 hours and at 50 C. for 1 hour. Thecooled reaction mixture was poured into ice water and the aqueousmixture extracted with ether. The combined ether extracts were washedtwice with water, once with saturated salt solution, and dried overmagnesium sulfate. Evaporation of the solvent at reduced pressureyielded 7.2 g. (88%) of 3-coumaranol. V

(b) 5-methoxy-3-coumaranol: 1.26 g. (0.045 mol.) of sodium hydride (as a61% mineral oil dispersion) and 7 g. (0.032 mol.) oftrimethyloxosulfonium iodide in 35 ml. of dry dimethyl sulfoxide wastreated with a solution of 4.56 g. (0.030 mol.) ofS-methoxysalicylaldehyde in ml. of dimethyl sulfoxide. Chromatographicpurification gave 1.6 g. (32%) of 5-methoxy-3-coumaranol: ir(neat)'2.98,3.4, 6.73, 8.8, 9.74, 10.4,u; nmr(CCl q- 2.33.5 (multiplet, aromatic)4.92 (multiplet, CEOH), 5.72 (multiplet, -'CI 6.4 (singlet, OCE 7.2(singlet, OH).

lIl) Preparation of alcohols having unsaturated linkages extending fromthe cyclopentyl ring structure is by the derivatization of certaincommercially available materials as follows:

(a) Allethrolone Step 1.Allethrin semicarbazone: The procedure describedby La Forge et al., J. Org. Chem., 19, 457 (1954), was employed. Asolution of 21.2 g. of allethrin (obtained as 20% solution in kerosenefrom Fairfield Chemical and purified as described by Barthel et al.,Soap, 20 (7), 121 (1944), in 72 ml. EtOH and 8 ml. pyridine was treatedwith a solution of 10 g. of semicarbazide hydrochloride in 12 ml. H O.The resulting solution was allowed to stand at room temperature 50hours. The 'EtOH was removed at reduced pressure and the resultantaqueous residue was added to water and extracted with ether. Thecombined ether extracts were washed with 5% H01 followed by brine untilneutral. The etheral extract was dried (MgSO and concentrated to yield25.1 g. of light yellow tafiy-like gum which was pure enough for furtherreactions.

Step 2.--Allethrolone semicarbazone: A solution of 25.1 g. of crudeallethrin semicarbazone in 75 ml. of MeOH under an N atmosphere wascooled to 0 C. in an ice bath and treated with a solution of 4.35 g. ofsodium methoxide in 75 ml. MeOH. The reaction was stored in therefrigerator 6 days and subsequently filtered to afford 15 g. of solid.An additional 3 g. was obtained by removing most of the solvent andcooling overnight. The total solid was recrystallized from EtOH/TtOAc toyield 9.90 g. (68%) M.P. -5 C. and 0.7 g. (5%) M.P. 1905 C. Thismaterial was found suitable for further use.

Step 3.Allethrolene (5): A mixture of 10.6 g. of allethrolonesemicarbazone and 58 g. of KHSO in 117 ml. H 0 and 77 ml. ether wasstirred under a nitrogen atmosphere for 24.5 hours. The layers wereseparated and the aqueous layer washed several times with ether. Thecombined ether extracts were washed once with brine, dried (MgSOconcentrated, and distilled giving 6.96 g. of allethrolone: B.P. 9395 C.(0.01 mm.); n 1.5120; IR (neat) 2.93, 3.42, 5.87, 6.05, 7,21,1r; nmr(CDCl 1- 4.30 (m, 1, CH C H =CH 5.1 (m, 4, GgOE, CH CH=Cg 7.10 (d, 2,i=6 Hz, -CH -C=CH [7.3 (3, 1, 1:6 Hz.), 7.7 (s, 1) C ]E CO], 7.9 (s, 3,=CHCI Glc analysis showed allethrolone to be 95% pure. Nmr was found tobe in agreement with the literature spectrum.

(IV) 5-benzyl-3-furfuryl methanol: A detailed description for thepreparation of this alcohol is described by M. Elliott et al., Nature,213, 493 (1967), incorporated herein by reference.

Preparation of the compounds of this invention is accomplished byesterification of 3-(2,2-tetramethyleneethenyl)-2,2-dimethylcyclopropanecarboxylic acid or an acid halidethereof with an alcohol. The esterification step of the presentinvention can be effected in various ways. The alcohol can be heatedwith the carboxylic acid in the presence of a strong acid, such as anaromatic sulfonic acid or sulfuric acid, in an organic solvent capableof azeotropically boiling with water, thereby removing the water formedin the esterification. The alcohol can also be heated with a lower alkylester of the carboxylic acid in the presence of a basic catalyst such assodium hydroxide, potassium hydroxide, sodium alcoholate, or potassiumalcoholate, and the like, continuously removing the lower alcohol formedthrough transesterification of the reaction system. In such case,methyl, ethyl, n-propyl and iso-propyl esters are suitable. In the mostpreferable esterification, the alcohol is treated with the carboxylicacid halide in an inert organic solvent, preferably in the presence ofan agent such as pyridine, triethylamine and other suitable amines, suchthat the esterification proceeds with the isolation of a hydrohalic acidsalt within a short period of time. For this purpose, the acid chlorideis the most preferred, though the acid bromide and the acid iodide canbe employed. Preparation of 3 (2,2 tetramethylene ethenyl) 2,2dimethylcyclopropanecarboxylic acid chloride by reaction with thionylchloride, along with the final esterification reaction leading to one ofthe preferred compounds of this invention, is illustrated by Example I.

EXAMPLE I Step 1.-Trans 3 (2,2 tetramethylene ethenyl) 2,2dimethylcyclopropanecarboxylic acid chloride: A solution of 4.4 g. ofthe parent acid prepared as described supra in hexane was converted toits acid chloride by refluxing with an excess of SOCl in n-hexane for 5hours in an N, atmosphere. Distillation yielded 3.82 g. (90%) ofcolorless acid chloride: -B.P. 7477 C. (0.26 mm.) IR(neat) 3.4, 5.6,9.45

Step 2.Ester of trans 3 (2,2 tetramethylene ethenyl) 2,2dimethylcyclopropanecarboxylic acid and allethrolone: A mixture of 3.82g. of 3 (2,2 tetramethylene ethenyl) 2,2-dimethylcyclopropanecarboxylicacid chloride in 16 ml. benzene and 2.85 g. pyridine was treated with 3g. of allethrolone in benzene solvent at C., rising thence to roomtemperature for 24 hours, allunder an N blanket. Work up from saturatedNaHCO drying (MgSO and concentration yielded 5.94 g. (100%) of desiredester: IR (neat) 3.38, 5.77, 5.82, 8.7 14 nmr (CCl;) '7' 4.4 (m, 2, CEO-and -Cg=CH 5.1 (m,'3, CH=C1E[ and.-C]g=), 7.1 (d, 2, J=6 Hz., -Cg CH=),8.05 (s, 3, =CH-C 8.8 and 8.88 [2s, 6, C(CE mass spectrum parent ion, m/e 328.

EXAMPLE II 2 indanyl ester of trans 3 (2,2 tetramethylene ethenyl) 2,2dimethylcyclopropanecarboxylic acid: Substitution of an equimolar amountof 2-indanol, prepared as hereinbefore described, for the allethroloneof Example I, Step 2, results in the formation of the 2- indanyl esterof trans 3 (2,2 tetramethylene ethenyl)-2,Z-dimethylcyclopropanecarboxylic acid.

EXAMPLE III Hydrogenated Z-idanyl ester of trans 3 (2,2 tetramethyleneethenyl) 2,2 dimethylcyclopropanecarboxylic acid: Substitution of anequimolar amount of 4,5,6,7- tetrahydro 2 indanol, prepared ashereinbefore described, for the allethrolone of Example I, Step 2,results in the formation of the 4,5,6,7-tetrahydro-2-indanyl ester oftrans 3 (2,2 tetramethylene ethenyl) 2,2 d imethylcyclopropanecarboxylicacid.

EXAMPLE 1v 3 coumaranyl ester of trans 3 (2,2 tetramethylene ethenyl)2,2 dimethylcyclopropanecarboxylic acid: Substitution of an equimolaramount of 3 -coumaranol, prepared as hereinbefore described, for theallethrolone of Example I, Step 2, results in the formation of the 3-coumaranyl ester of trans-3-(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid.

EXAMPLE V EXAMPLE VI -ethyl-2-indanyl ester of trans-3(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid:Substitution of an equimolar amount of 5 ethyl-Z-indanol, prepared ashereinbefore described, for the allethrolone of Example I, Step 2,results in the formation of the S-ethyl- Z-indanyl ester of trans-3-(2,2tetramethylene ethenyl) -2,f Z-dimethylcyclopropanecarboxylicgacid;

EXAMPLE-VII 5-methoxy-3-coumaranyl ester of trans-3 (2,2 tetra-.methylene ethenyl) 2,2-dimethylcyclopropanecarboxylic acid: Substitutionof an equimolar amount of S-methoXy S-coumaranol, prepared ashereinbefore described, for the allethrolone of Example I, Step 2,,results in the formation of the 5-methoxy-3-coumaranyl ester oftrans-3-(2,2- tetramethylene ethenyl) 2,2 dimethylcyclopropanecarboxylic acid. r

' EXAMPLE VI'II j ,1,

5-nitro-2-indanyl ester of trans-3 (2,2-tetramethylene; ethenyl)2,2-dimethylcyclopropanecarboxylic acid: Substitution of an equimolaramount of S-nitro-Z-indaxiol, prepared as hereinbefore described, forthe allethrolone of Example I, Step 2, results in the formation of'the15-1.:

nitro-2-indanyl ester of trans-3 (2,2 tetramethylene.ethenyl)-2,2-dimethylcyclopropanecarboxylic acicL. 3

EXAMPLE IX 5-ch1oro-3-coumarany1 ester of trans-3- (-2,j2'-tetrameth-'vylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid:

Substitution of an. equimolar amount of $-cliloro-3'-cou-. maronal,prepared as hereinbefor'e described, for the ale lethrolone of ExampleI,Step 2, resultsjin 'theformation' of the 5-chloro-3-coumaranyl ester oftrans-3 (2,2-tetramethylene ethenyl) 2,2-dimethylcyclopropanecarboxylicacid. 7

EXAMPLE X Cinerolone ester of trans 3-(2,2-tetrainethyleneethe nyl)2,2-dimethylcyclopropanecarboxylic acid: S'ubstitu-- tion of anequimolar amount of cinerolone, prepared as hereinbefore described, forthe allethrolone of Example I,

Step 2, results in the formation of the cinerolone ester; of trans-3(2,2 tetramethylene etheuyl)-2,2 -'dimethyl-,

cyclopropanecarboxylic acid.

EXAMPLE XI Exa'mple'I, Step 2, results in the formation ofthe5-amino.

2 -indanyl ester of trans-3-(2,2-tetramethylene et henyl )"-2,

2-dimethylcyclopropanecarboxylic acid.

EXAMPLE x11 5-phenyl-3-coumaranyl ester :of trans-'3-(2,2-tetramethyleneethenyl)-2,2-dimethylcyclopropanecarboxylic acid;

Substitution of an equimolar amount of .5 -pheny1-3-c0u,-'- maranol,prepared as hereinbefore described, for the allethrolone of Example I,Step 2, results in the formation of the 5-phenyl-3-coumaranyl ester oftrans'-3- 2,2 -tet ra-:

methylene acid.

In each of the foregoing examples, the mixture of the ethenyl)2,2-dimethylcyclopropanecarboxylic;

cis and trans isomers of the acid chloride of 3- (2,2 tetral methyleneethenyl) 2,2-dimethylcyclopropanecarboxylie acid is substituted for thetrans isomer,- yielding mixtures of the cis and trans esters of ExamplesI through XII.

While the novel esters of the present invention are all insecticidal andelfective incontrolling insect infesta-- tion, the following compoundsare preferred for their superior insecticidal properties:

The Z-indanyl ester of trans-3-(2,2-tetramethylene e thenyl)2,2-d1methylcyclopropanecarboxylic acid: the 3::

coumaranyl ester of trans-3-(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid: the I5-benzyl-3-f furfu'rylmethanol ester of trans-3-('2,2-'tetramethyleneethenyl)-2,2-dimethylcyclopropanecarboxylic acid: and the allethroloneester of trans-3-(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid.

The dextrorotatory and levorotatory forms of the ester conformers, andthe racemates thereof, are embodiments of the present invention.

The novel compounds of this invention have superior properties relativeto corresponding chrysanthemic acid esters, which is believed to be dueto enhanced resistance to detoxification achieved by modification of theisobutylone system of pyrethrin-like insecticides. Example XIH belowdemonstrates the markedly enhanced insecticidal activity of the estersof this invention relative to esters of chrysanthemic acid. A comparisonof the insecticidal activity with that of pyrethrum is also presented.

EXAMPLE XIII n Insecticidal compositions comprising the allethroloneester of trans-3 (2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid from Example I, dissolved in acetone and dispersed indistilled water with Triton X--100 emulsifier. Similar compositionscomprising pyrethrum and cis-trans-allethrin, respectively, were alsoprepared. These compositions were separately applied for a ten secondperiod to houseflies retained in a 2" x 5" diameter screened cage. Thesprays were applied from the Waters vertical spray tower operating atp.s.i. and discharging about 30 ml. of material per minute through anatomizer. The spray descends through an 8" stainless steel cylinder totest insects below the atomizer. The insects were retained in thesprayed cages for mortality observations. Test compositions having theindicated percentage concentration of weight (w.) of test compound tospray volume (v.) were utilized in the tests. The results are set forthin Table 1 below.

TABLE 1.HOUSEFLY TESTS-KNOCK-DOWN AND KILL Average percent Knock-Mortaldown Percent (10 Ester w./v. minutes) 1 Plperouyl butoxide (PB),an insecticidal synergist, has essentially no insecticidal activity atthe concentrations reported above.

As can be seen from the foregoing example, a representative compound ofthis invention possesses excellent insecticidal properties.Additionally, the compounds of the instant invention are substantiallyless toxic to mammals than are most common insecticides.

Similar results are secured when each of the esters of Examples IIthrough XII is incorporated in the insectici dal composition of ExampleXIH in place of the allethrolone ester.

The compounds of the instant invention are insecticidally effective whentested against a wide variety of insects including the Southern armyworm, the Mexican bean beetle, the pea aphid, the mite, the Germancockroach, the adult mosquito, adult stable flies, black carpet beetlelarva, webbing clothes moth larva, adult rice weevils, and adultsawtooth grain beetles,

Insecticidal compositions containing the esters of the present inventioncan be formulated and utilized as oil solutions, emulsifiableconcentrates, wettable powders, dusts, aerosols, or impregnated intowood, fabrics, etc., and provide a long lasting residual efiect. Suchcompositions can include the generally employed carriers or diluents andauxiliary agents which are well-known to those Isoocty1 phenylpolyeflroxy ethanol OPE 9'10 nu lied by Rohm 8; Haas Company. pp

a es

' of the invention normally comprise up to about 10% .by

weight of such dust formulations. An amount of up to about 3% ispreferred and is suitable formost applications.

Likewise, suspensions or dispersions of the compounds in a non-solvent,such as water, may be suitably employedfor the treatment of foliage.'Also suitably employed are solutions of the insecticides of theinvention in oil which is emulsified in water. Examples of oil solventsinclude hydrocarbons such as benzene and toluene, halogenatedhydrocarbons such as chlorobenzene, chloroform, fluorotrichloromethaneand dichlorodifluoromethane, and commercial mixtures of hydrocarbonssuch as the common Stoddard solvents, petroleum ethers, and the like.

Aerosols can be prepared by dissolving compounds of the invention in ahighly volatile liquid carrier such as trifluorochloromethane,nitromethane, dichlorodifluoroethane and the like, or by dissolving suchcompounds in a less volatile solvent, such as benzene or kerosene, andadmixing the resulting solution with a highly volatile liquid aerosolcarrier such as the polyfluorohydrocarbons commonly used as aerosolpropellants.

The novel compounds of the invention are useful for destroying a varietyof insects. Accordingly, a method as pect of the present inventioncomprises combating insects by applying to insects or to an insecthabitat one or more of novel compounds of the invention.

Preferably the esters of this invention are employed in combination witha synergistic agent, for example, piperonyl butoxide, piperonylsulfoxide, fi-butoxy-;8-thiocyanodiethyl ether and the like.

What is claimed is: 1. A compound having the structure CH8 on, CH -Cg!wherein R is a member selected from the group consisting of and and R isa member selected from the group consisting of hydrogen, chlorine,methyl, ethyl, propyl, methoxy, ethoxy, propoxy, phenyl, N0 and NH 2. Acompound in accordance with claim 1 which is a 2-indanyl ester of3-(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid.

3. A compound in accordance with claim 1 which is a hydrogenatedZ-indanyl ester of 3-(2,2-tetramethyleneethenyl)-2,Z-dimethylcyclopropanecarboxylic acid.

4. A compound in accordance with claim 1 which is a 3-coumaranyl esterof 3-(2,2-tetramethylene ethenyl)-2,2- dimethylcyclopropanecarboxylicacid.

5. A compound in accordance with claim 1 which is a S-ethyl-Z-indanylester of 3-(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylic acid.

6. A compound in accordance with claim 1 which is a 5 methoxy 3coumaranyl ester of 3 (2,2 tetramethylene ethenyl) 2,2dimethylcyclopropanecarboxylic acid.

" compound in accordance with claim 1 which is a N f v R fer'nces Citcd7 5fnitro 2 indz'myl est er 'of 3 (2,2 tctramethylene V U ethenyl 2,2dimethylcyclopropanecarboxylicacid. UNITED A F' A E I 8 A compound inaccordance with claim 1 which is a 3,538,143 1 7 M at a] 260-468 5chloro 3 copmaranyl ester of 3-(2,2-tetra methylene 5 1 V 1 jQTHER R N Qf 11methYlCWbPmPanecarbxY11 acld' Elliot et .aL'Na ture 213 5075 493-4(1967).-

9. A compound in accordance. with claim 'lgwhichis a A 5 a'mino 2indanyl estet'of 3 (2,2 tetramethylcne HENRY U S" E e thenyl) 2,2dimethylcyclopropanecarboxylic acid.

, 10.'A compound in accordancc with claim 1 which is a 10- OD Exammer 5l phenyl 3'- coumaranyl ester of 3 -(2 ,2 -t6 t[3 me thy1-. v U S l XRcue ethcnyl)p2,}dimcthylcyclopropanecacbonlic gc'jd; j 1

v g j 260 -48P;424285 ,3'06'

